Block polymers containing a poly(aryl ether ketone) and methods for their production

ABSTRACT

Described herein are crystalline block polymers and chain extended polymers containing blocks of crystalline poly(aryl ether ketones). Also, described herein are monomers and oligomers suitable for preparing the crystalline block polymers and chain-extended polymers. Further, described herein are methods for producing the crystalline block and chain-extended polymers, as well as the monomers and oligomers.

This is a division of application Ser. No. 729,580, filed 5/2/85, nowU.S. Pat. No. 4,774,296.

FIELD OF THE INVENTION

This invention is directed to novel solution polymerized crystallineblock polymers containing blocks of crystalline poly(aryl etherketones). This invention is also directed to novel monomers andoligomers. Also described herein are methods for producing thesolution-polymerized crystalline block polymers, the monomers and theoligomers.

BACKGROUND OF THE INVENTION

Over the years, there has been developed a substantialy body of patentand other literature directed to the formation and properties ofpoly(aryl ethers) (hereinafter called "PAE"). Some of the earliest worksuch as by Bonner, U.S. Pat. No. 3,065,205, involves the electrophilicaromatic substitution (e.g. Friedel-Crafts catalyzed) reaction ofaromatic diacylhalides with unsubstituted aromatic compounds such asdiphenyl ether. The evolution of this class to a much broader range ofPAE's was achieved by Johnson et al., Journal of Polymer Science, A-1,vol. 5, 1967, pp. 2415-2427, Johnson et al., U.S. Pat. Nos. 4,108,837and 4,175,175. Johnson et al. show that a very broad range of PAE can beformed by the nucleophilic aromatic substitution (condensation) reactionof an activated aromatic dihalide and an aromatic diol. By this method,Johnson et al. created a host of new PAE's including a broad class ofpoly(aryl ether ketones), hereinafter called "PAEK's".

In recent years, there has developed a growing interest in PAEKs asevidenced by Dahl, U.S. Pat. No. 3,953,400; Dahl et al., U.S. Pat. No.3,956,240; Dahl, U.S. Pat. No. 4,247,682; Rose et al., U.S. Pat. No.4,320,224; Maresca, U.S. Pat. No. 4,339,568; Atwood et al., Polymer,1981, vol. 22, August, pp. 1096-1103; Blundell et al., Polymer, 1983vol. 24, August, pp. 953-958, Atwood et al., Polymer Preprints, 20, no.1, April 1979, pp. 191-194; and Rueda et al., Polymer Communications,1983, vol. 24, September, pp. 258-260. In early to mid-1970, RaychemCorp. commercially introduced a PAEK called STILAN™, a polymer whoseacronym is PEK, each ether and keto group being separated by1,4-phenylene units. In 1978, Imperial Chemical Industries PLC (ICI)commercialized a PAEK under the trademark Victrex PEEK. As PAEK is theacronym of poly(aryl ether ketone), PEEK is the acronym of poly(etherether ketone) in which the 1,4-phenylene units in the structure areassumed.

Thus PAEKs are well known; they can be synthesized from a variety ofstarting materials; and they can be made with different meltingtemperatures and molecular weights. The PAEKs are crystalline, and asshown by the Dahl and Dahl et al. patents, supra, at sufficiently highmolecular weights they can be tough, i.e., they exhibit high values (>50ft-lbs/in²) in the tensile inpact test (ASTM D-1822). They havepotential for a wide variety of uses, but because of the significantcost to manufacture them, they are expensive polymers. Their favorableproperties classes them in the upper bracket of engineering polymers.

PAEK's may be produced by the Friedel-Crafts catalyzed reaction ofaromatic diacylhalides with unsubstituted aromatic compounds such asdiphenyl ether as described in, for example, U.S. Pat. No. 3,065,205.These processes are generally inexpensive processes; however, thepolymers produced by these processes have been stated by Dahl et al.,supra, to be brittle and thermally unstable. The Dahl patents, supra,allegedly depict more expensive processes for making superior PAEK's byFriedel-Crafts catalysis. In contrast, PAEK's such as PEEK made bynucleophilic aromatic substitution reactions are produced from expensivestarting fluoro monomers and thus would be classed as expensivepolymers.

In all of the above described U.S. Patents, the copolymers that aredescribed are random or ordered copolymers characterized in that all ofthe repeat units of the polymer are derived from monomers and aretypically distributed randomly along the polymeric chain.

European patent application 125,816, filed Apr. 19, 1984, based forpriority upon British patent application 8,313,110, filed May 12, 1983,is directed to a method for increasing the molecular weight by meltpolymerization of a poly(aryl ether) such as PEEK.

The process of European patent application 125,816, provides a basis bymelt polymerization above the crystalline melting point of the poly(arylether) to increase the molecular weight by chain extension of polymerblocks. The application theorizes that the procedure can be used formaking the block copolymers described in U.S. Pat. Nos. 4,052,365 and4,268,635. Implicit problems associated in the process of thisapplication are the difficulty in controlling the molecular weight ofthe resulting polymer and/or limiting isomerization and the problemsassociated with branching. The process of this European applicationwould appear to be advantageous in making composites where the linearityand solution properties of the final polymer are not so critical.

PAEK block copolymers have been described in U.S. Pat. Nos. 4,052,365and 4,268,635. U.S. Pat. No. 4,052,365 describes random or blockcopolymers having repeating units of the structure --Ar--O--AR--CO-- and--Ar--O--Ar--SO₂ --. The patent states that these block copolymers arecrystalline. U.S. Pat. No. 4,268,635 describes a process for preparingpolymers containing --Ar--O--Ar--SO₂ -- and --Ar--O--Ar--CO-- unitswhich the patentee believes to contain block structures. The patentstates that the polymers are crystalline and exhibit improved hightemperature properties compared with totally random copolymers ofsimilar composition. However, the block copolymers in said patentsrequire units with --SO₂ -- linkages. The --SO₂ -- linkage tends tobreak up the crystallinity of the polymer which results in inferiorproperties as compared to polymers which do not contain the --SO₂ --linkage but have ether and/or keto groups instead. Due to the amorphousnature of the sulfonyl containing component used in making these priorart block copolymers, lower rates of crystallization are induced andhence, their commercial utility is less than desirable. The --SO₂ --component so adversely affects the crystallinity properties that thereis a maximum limit in the T_(m), far below that for the block polymersof this invention. A further deficiency of these prior art blockcopolymers is that they cannot be used to form compatible blends withother PAEKs.

THE INVENTION

This invention comprises solution-polymerized block polymers wherein thecomponents of the block structure are tough crystalline poly(aryl etherketone)s (PAEK's). The block contains essentially ether groups (--O--)joined to keto groups (--CO--) through 1,4-phenylene groups. Thisinvention is also directed to monomers and oligomers which are suitablefor making the block copolymers. Also, this invention is directed tomethods for making the monomers, the oligomers and the block copolymers.

The block polymers of this invention are tough, crystalline and have agood combination of physical and mechanical properties.

The block is bonded to another block of the same or differentcomposition through one or more of an ether group, a keto group, or adivalent copolymeric chain extending unit. In the case where the blocksare the same, bonding is effected through a divalent monomer, dimerunit, or oligomeric unit connecting the blocks through ether groups toproduce a copolymeric structure. In the preferred embodiment, with thepossible exception of when the blocks are connected through a divalentchain extending single unit, the poly(aryl ether ketone) comprisesessentially ether and keto groups joined through 1,4-phenylene groups.The block polymers of this invention preferably have a reduced viscosityof at least 0.9 dl/g as measured in sulfuric acid at 25° C.(concentration of 1 gm/100 ml).

The solution-polymerized polymers of this invention contain oligomericblocks that are interconnected. The oligomeric blocks are homopolymersand copolymers having a chain length such that the number of merstherein is at least two. If two or more different oligomeric blocks aredirectly interconnected the polymers of this invention fall into thecategory of block polymers as defined in polymer chemistry. The polymersas defined herein can also contain two or more similar or identicalblocks connected by a monomeric or oligomeric coupling unit, with theproviso that when the blocks are identical the coupling unit must becopolymeric. As a result, by reason of the coupling unit, the finalmaterial is a copolymer even though identical blocks are being joined.

In more specific terms, this invention comprises two classes ofsolution-polymerized block polymers, to wit, block copolymers and chainextended copolymers. In the case of the block copolymers, they are ofthe classical A--B, A--B--A, (AB)_(n), A--B--C, etc., types. The chainextended copolymers are typically characterized by the structureA--x--A--x-- wherein A is a block unit, all the A's can be the same ordifferent and x is the chain extending monomer or dimer. When x is alarge unit, for example, an oligomer, then for the purposes of thisinvention, the polymer would be classed a block copolymer. Further, xand A must be different structural units.

Block units, according to this invention, comprise oligomeric sizestructures, i.e., structures which contain at least two monomer units insequence. Chain extending units comprise structures which are smallerthan oligomeric, i.e., they are preferably monomer and dimer structures.

The PAEKs of this invention are characterized by a toughness measured asa tensile impact strength of greater than 50 ft-lbs/in² andcrystallinity characterized by a distinct crystalline meltingtemperature (T_(m)) which is at least 100° C. greater than its secondorder glass transition temperature (T_(g)).

It should be understood that the crystalline block copolymers of thisinvention may involve randomization due to transetherification duringthe solution polymerization reaction. Ether links formed duringpolymerization are sufficiently reactive due to activation by adjacentketone links to react with phenolic reactants and this leads to randomchain scission at the ether links adjacent to the ketone links, andre-assembling. Ether links sandwiched between two ketone links areparticularly susceptible to this scission reaction. This is well knownin the art. See Atwood et al, British Polymer Journal, 1972, 4, 391-399;Atwood et al, Polymer, 1981, 22 August, 1096-1103. The rate oftransetherification, however, is low in comparison to that of a typicalnucleophilic polycondensation reaction, hence, the use of appropriatestarting materials leads to the solution-polymerized block polymers ofthis invention. On the other hand, when two precursor blocks are reactedvia solution-polymerized transetherification to yield the blockcopolymer, the reaction can easily be stopped at the block copolymerstage prior to total randomization.

The solution-polymerized block polymers of this invention aredistinctive from those in the prior art by virtue of their enhancedlinearity. This results in polymers which possess maximum crystallinity,crystallization rates and low viscosity to high performancecharacteristics. The solution-polymerized block polymers of thisinvention are made at relatively low temperatures, typically not inexcess of 300° C. even under the most aggressive polymerizationconditions, and this is contrasted with temperatures of 400° C. whichare utilized in melt-polymerization procedures for chain extension ofpolyaryletherketones into polymer blocks (see European patentapplication 125,816, supra). Consequently, solution polymerizationproceeds with minimal branching and isomerization, resulting in apolymer which provides the most favorable property characteristics.

DETAILED DESCRIPTION OF THE INVENTION

There are many varieties of PAEKs and they are made by one of twoprocesses, viz. electrophilic and nucleophilic aromatic substitutionreactions. The former is mainly achieved through Friedel-Craftscatalysis and has the advantage of allowing the use of relatively lowcost starting materials such as terephthaloyl chloride, diphenyl etherand phosgene, but suffers in the past from the necessity to employcorrosive solvents such as HF and the existence of too much branching inthe polymer structure. Nucleophilic aromatic substitution,unfortunately, requires the use of expensive fluorine substitutedmonomers such as difluorobenzophenone to achieve PAEKs with desirableproperties. Alternative routes or alternative structures which can lowerthe cost of manufacture and/or improve the polymer properties wouldprovide great advantages.

A facet of PAEK technology is that the crystalline melting point can befairly accurately determined from the ether to keto (or ketone) ratio inthe polymer. As the ratio goes up, the Tm goes down. There is apractical limit to a suitable Tm; that is the temperature at which thepolymer must be molded and the degradation temperature of the polymer.If the molding temperature is at the degradation temperature, andsufficient polymer flow is not obtainable below that temperature, thenthe PEAK's Tm is too high. This means that the ether to keto ratio istoo low and must be raised. Such can be achieved by increasing the ethercontaining and/or forming component in the polymer manufacture at theexpense of the keto containing component. Increasing the ether contenttends to increase the toughness of PAEKs and a dramatic alteration inthe ether to keto ratio will provide noticeable changes in toughness.The tools for doing this are well within the capabilities of the skilledchemist knowledgeable of the techniques of electrophilic andnucleophilic aromatic substitution reactions. The displacement of thesegroups along the linear chain of the polymer is not believed to benarrowly critical to achieving the Tm and Tg properties.

The Forming Reactions

One of the attributes of this invention is that the ultimate blockpolymer will be made from a PAEK starter molecule (block precursor)which is oligomeric to significantly polymeric. As a rule, the PAEKstarter molecule has a low enough molecular weight that it has a reducedviscosity below about 0.9 dl/g, as measured in concentrated sulfuricacid at 1 g/100 ml at 25° C. It is thus reacted with reactants which canform the other block or the chain extension between blocks by solutionpolymerization; indeed it is possible to combine the steps of blockpolymer or of chain extension in the same solution polymerizationreaction. In this way a block polymer or a chain extended polymer havinga reduced viscosity greater than 0.9 dl/gm. (as measured in concentratedsulfuric acid at 1 g/100 ml at 25° C.) is obtainable.

An important step in the block polymer synthesis is the preparation ofthe precursor blocks. This can be done by any of the knownsolution-polymerization procedures for making PAEK, except that thestoichiometry is selected such that the precursor's molecular weight iscontrolled and the precursor is end-capped with functional groupsavailable for block copolymerization/chain extension reactions. However,if transetherification is the preferred route to block polymerformation, then the precursor need not require the presence offunctional capping groups as such. Thus, the precursor can be formedfrom conventional reactants and by using conventional methods.

For example, by the electrophilic aromatic substitution reaction, anacid halide can be reacted with a wholly functionally aromatic organiccompound to produce a host of PAEK precursor molecules. With just twomonomers and a capping agent, and using such a technique, a host ofhalide terminated or oligomer precursors are possible. To illustratethis point, one may combine phosgene, diphenyl ether and terephthaloylhalide, with the capping agent p-fluorobenzoyl chloride, into manyunique combinations. For example*:

*(In the following equations Ph is a phenyl or a 1,4 phenylene unit withthe provision that where there are two carbonyl groups attached to thesame phenyl ring up to 50% of these groups may be in the 1,3 position toeach other. Of course, some 1,2- and 1,3-phenylene units can also beformed in the electrophilic substitution process.) ##STR1##

The above variety can be extended significantly by substituting a hostof other aromatic compounds, thus described by Dahl and Dahl et al.,supra, such as diphenoxybenzene, diphenoxybenzophenone, 4,4'-diphenoxybiphenyl, and the like, for part or all of the diphenyl ether. Obviouslyn need not be a very large number to provide a weight average molecularweight which achieves a reduced viscosity of at least 0.9 dl/g.

The fact that very useful block polymers made by this invention canutilize lower molecular weight block precursors is most desirableespecially when the precursor is made by the electrophilic aromaticsubstitution reaction as above described. Such lower molecular weightprecursors are more readily washed of the catalyst such that theresulting block polymer is cleaner and less prone to unwanted branchingreactions during the final polymerization to the block polymer. It isthus an important feature of this invention that one is able to utilizeprecursors made by the electrophilic process (e.g. Friedel-Craftsreaction). Polymers with unique structures, displaying excellenttoughness and thermal stability can be prepared in this manner.

Moreover, since the precursor is not a very high molecular weightspecies, less stringent temperature conditions and thus even volatilesolvents may be used to prepare such precursor. This in turn can resultin such benefits as better color and less branching. Of course,crystallization will be an ever present problem, and temperature andsolvent selection will be dictated by this factor if the molecularweight chosen for the precursor creates such a problem. Needless to say,the options available to achieve successful polymer formation arenumerous and in no way confining to only the procedures of the prior artfor making the polymers of the prior art.

However, what is most desirable from the standpoint of PAEK manufacture,is that much of the block polymer can be derived from low cost startingmaterials such as phosgene, diphenyl ether and terephthaloyl chloride.

On the other hand, the block precursor may be made according, e.g., toReactions A-C above without the fluorinated capping agent. In such acase, alteration in the stoichiometry will provide acyl halide endgroups useful for further reactions. In summary, therefore, theprecursors can be tailored such that the desirable block polymers can beformed by both electrophilic and nucleophilic aromatic substitutionreactions. Thus, the variety of procedures for making the block polymersof this invention are many, and unconventional techniques may beavoided.

For example, the precursors A', B', and C' prepared as shown above canbe converted into block polymers using one or more of, for example,4,4'-difluorobenzophenone, bis-p-(p-fluorobenzoyl) benzene, hydroquinoneand/or biphenol; viz: ##STR2##

It should be appreciated that transetherification as discussed abovewill make the simplistic characterization of the block polymers muchmore complex, but the overall block structure should prevail imposing asignificant structural difference from the PAEKS of the prior art.

The block precursors A-C and A'-C' above can be reacted by a furtherelectrophilic aromatic substitution reaction to produce block polymersof this invention. In the preferred practice of this invention, theblock precursors are made by either electrophilic or nucleophilicaromatic substitution reactions and the final polymerization to theblock polymer is accomplished by the nucleophilic route. But it is ofcourse also possible to employ electrophilic aromatic substitutionreactions for both the precursor and final block polymerizations. Thismay be illustrated as follows: ##STR3##

The PAEK block precursors

The crystalline PAEK block precursors which are suitable for forming theblock copolymer with the exception of the end blocking portion can begenerically characterized as containing repeating units, exclusive ofthe terminating groups, of one or more of the following formulae:##STR4## wherein Ar is independently a divalent aromatic radical such asphenylene or biphenylene, X is independently O, ##STR5## or a directbond and n is an integer of from 0 to 3, b, c, d, and e are 0 to 1 and ais an integer of 1 to 4 and preferably d is 0 when b is 1.

Preferred block precursors include those having repeating units of theformulae: ##STR6##

The nucleophilic method comprises heating a solvent solution of amixture of at least one bisphenol and at least one dihalobenzenoidcompound and/or at least one halophenol compound in which the halogenatoms are activated by CO groups ortho or para thereto in the presenceof a base such as an alkali carbonate as described in, for example,Canadian Patent No. 847,963 and U.S. Pat. No. 4,176,222. In making theprecursor, one of the reactants is used in excess to provide afunctional terminal group. The amount of such excess is used to controlthe molecular weight of the precursor. Alternatively, equimolar amountsof reactants can be used; in such case molecular weight (or extent ofreaction) is controlled by stopping the reaction after a well-definedperiod of time.

Preferred bisphenols in such a process include:

4,4'-dihydroxybenzophenone,

4,4'-dihydroxybiphenyl, and

4,4'-dihydroxydiphenyl ether.

Phenols such as hydroquinone may also be used.

Preferred dihalobenzenoid and halophenol compounds include:

4-(4-chlorobenzoyl)phenol,

4-(4-fluorobenzoyl)phenol,

4,4'-difluorobenzophenone,

4,4'-dichlorobenzophenone,

4-chloro-4'-fluorobenzophenone,

1,4-bis(4-fluorobenzoyl)benzene,

1,3-bis(4-fluorobenzoyl)benzene,

4,4'-bis(4-fluorobenzoyl)diphenylether, and

4,4'-bis(4-fluorobenzoyl)diphenyl.

Also, PEAK block precursors such as those containing repeating units ofthe formula: ##STR7## may be produced as described above byFriedel-Craft reactions utilizing hydrogen fluoride-boron trifluoridecatalysts as described, for example, in U.S. Pat. Nos. 3,953,400,3,441,538; 3,442,857 and 3,516,966.

Additionally, the precursors may be prepared by Friedel-Crafts processesas described in, for example, U.S. Pat. Nos. 3,065,205; 3,419,462;3,441,538; 3,442,857; 3,516,966; and 3,666,612. In these patents a PAEKis produced by Friedel-Crafts polymerization techniques usingFriedel-Crafts catalysts such as aluminum trichloride, zinc chloride,ferric bromide, antimony pentachloride, titanium tetrachloride, etc. anda solvent.

The precursor may also be prepared according to the processes asdescribed in, for example, U.S. Defensive Publication T 103,703 and U.S.Pat. No. 4,396,755. In such processes, reactants such as (a) an aromaticmonocarboxylic acid, (b) a mixture of at least one aromatic dicarboxylicacid, and an aromatic compound, and (c) combinations of (a) and (b) arereacted in the presence of a fluoroalkane sulphonic acid, particularlytrifluoromethane sulphonic acid.

Additionally, PAEK block precursors of the following formulas: ##STR8##may also be prepared according to the process as described in U.S. Pat.No. 4,398,020. In such a process,

(a) a mixture of substantially equimolar amounts of

(i) at least one aromatic diacyl halide of formula

    YOC--Ar--COY

where --Ar-- is a divalent aromatic radical, such as 1,4-phenylene, Y ishalogen, preferably chlorine, and COY is an aromatically bound acylhalide group, which diacyl halide is polymerizable with at least onearomatic compound of (a)(ii), and

(ii) at least one aromatic compound of the formula

    H--Ar'--H

wherein --Ar'-- is a divalent aromatic radical such as diphenyl ether,and H is an aromatically bound hydrogen atom, which compound ispolymerizable with at least one diacyl halide of (a)(i), or

(b) at least one aromatic monoacyl halide of the formula

    H--Ar"--COY

where --Ar"-- is a divalent aromatic radical such as diphenoxybenzene,and H is an aromatically bound hydrogen atom, Y is halogen, preferablychlorine, and COY is an aromatically bound acyl halide group, whichmonoacyl halide is self-polymerizable, and

(c) a combination of (a) and (b) is reacted in the presence of afluoroalkane sulphonic acid.

In all of the electrophilic routes described above, the precursormolecular weight is controlled using known techniques. The preparationmay, for example, be conducted in a solvent where precipitation takesplace after a given molecular weight is reached. Control of the reactiontime is another method to control precursor size. Many other methodsexist and are well known to those skilled in the art.

The term PAEK as used herein is meant to include homopolymers,copolymers, terpolymers, graft copolymers, and the like, providedcrystallinity of the PAEK is maintained. For example, any one or more ofthe units (I) to (V) may be combined to form copolymers, etc.

The Block Copolymers

The block copolymers may be depicted ideally as having the formula:##STR9## wherein the units A and B are a crystalline poly(aryl etherketone), a and b are integers of at least 1, preferably at least 2 andmost preferably at least 4, and c is an integer of 1 or greater,preferably from greater than 1 up to 100, and most preferably from 3 to90, X is a monomeric --Ar'"--O-- unit where Ar'" is a divalent aryleneradical such as p-phenylene or an oligomeric radical such as Ar""--O_(n)where n is at least two and can be up to about 50 and Ar"" is a divalentarylene group optionally containing carbonyl functions in its structure,i.e., Ar"" can be, for example, p-phenylene or ##STR10## and the like.Where the blocks are identical X must be an oligomeric group.

The preferred block copolymers ideally are of the following formulae:##STR11##

THE MOST PREFERRED EMBODIMENTS OF THE INVENTION

The most preferred embodiments of this invention comprise block polymersof the following formulae ##STR12## wherein "Ph" is as described above,x is a number of at least 1, preferably at least 3, to a value not inexcess of about 1000, a is a number having a value of at least 1,typically not in excess of 100, b is a number at least 1, preferablyhaving a value of at least 2, to a number not in excess of about 100,and Z is a chain extending group selected from one or more of thefollwing: ##STR13## wherein y has a value of at least 1 up to about 50,and z has a value of at least 1 up to about 50.

The Monomers and Oligomers

Novel monomers and oligomers which may be used herein are depicted bythe following formulae: ##STR14## wherein X is halogen, preferablyfluorine and n is an integer of from 1 to about 100.

The preferred monomers are represented by the following formulae:##STR15##

Preparation of the Block Copolymers and Monomers and/or Oligomers

The block copolymers of this invention may be prepared by one or more ofthe following solution polymerization processes. These processes utilizeprecursors prepared as follows:

Starting Materials

(I) Functionalized Starting Material prepared via the nucleophilicroute.

(A) Hydroxyl-terminated precursors.

The condensation of monomers such as listed above, i.e., the bisphenolsand dihalobenzenoids with optionally added halophenols, can be made toyield hydroxyl-terminated oligomeric precursors. The conditions used forthe preparation of these products are the same as set forth in thesection titled "Situation I", infra, except that an appropriate excessof the hydroxyl coreactant is used. The higher the excess of coreactant,the lower the molecular weight of the resulting polymer. For example, apolymer having a number average molecular weight of about 5,000 isobtained when one mole of diphenol is reacted with about 0.92 moles ofan activated dihalobenzenoid compound. A typical reaction is illustratedby the following: ##STR16##

Another route to the hydroxyl-terminated precursor is the reaction of anactivated halophenol with a diphenol as shown by the following:##STR17##

(B) Halogen-terminated precursors.

A similar condensation as described in (A) above is used except that anexcess of the activated dihalobenzenoid compound is reacted. Thedihalo-terminated precursor is illustrated by the following: ##STR18##

In another embodiment, the following reaction may be used: ##STR19##

Since there may be some hydrolysis during the reaction, as shown above,total dihalo termination is accomplished by adding a small additionalamount of the same dihalo compound (or optionally, any other activateddihalo compound) to the reaction mixture and heating for about 1 to 2hours.

(C) Halogen-hydroxy-terminated precursors

These precursors may be prepared by any of the following methods:

(i) Selective hydrolysis of one halo atom in (VII) above, or

(ii) The reaction of equimolar amounts of diphenol and dihalo-compounds.In this case reaction time is extremely important as it will eventuallycontrol the molecular weight of the precursor. The longer the reactiontime, the higher the molecular weight of the precursor. Shouldhydrolysis occur, termination may be carried out, as described under (B)above (i.e. via the addition of additional dihalo-compound); or

(iii) The reaction of precursor (VI) with a calculated amount of adihalobenzoid compound; or

(iv) The reaction of precursor (VII) with a calculated amount of adiphenol compound. The reaction conditions are as described underSituation I, infra.

(v) The reaction of a halophenol where, once again, the reaction time isvery important since it will control the molecular weight of theprecursor.

(II) Functionalized materials prepared via the electrophilic route

(A) Halogen-terminated

The preparation of these materials is illustrated by the reaction ofterephthaloyl chloride and diphenyl ether as follows: ##STR20##

Another embodiment using the same monomers is illustrated as follows:##STR21##

Another example is the reaction of diphenyl ether with phosgene asfollows: ##STR22##

Thus the polyketone oligomers may be prepared by reacting an excess ofeither (i) or (ii):

(i) at least one electrophilic halo acylhalide or diacyl halide of theformula: ##STR23## where --A-- is a direct bond or a divalent aromaticradical, Y is halogen and --COY is acylhalide, a is 0 or 1,polymerizable with at least one aromatic compound of (ii) below, and

(ii) at least one aromatic compound of the formula:

    H--Ar'--H

where --Ar'-- is a divalent aromatic radical and H is an aromaticallybound hydrogen atom, which compound is polymerizable with at least onehalo acylhalide or diacyl halide of (i), above, followed (when a is 1)by the Friedel-Crafts reaction of the obtained intermediate with Z--Ar⁵H if excess of (i) is used, or with Z--Ar⁵ COY if excess of (ii) isused. In the formulae above Z is halogen, preferably fluorine, Y is asdefined above, and Ar⁵ is a divalent, optionally alkyl or arylsubstituted arylene group.

Specifically, the precursors may be prepared by reacting any of thewell-known aromatic coreactants such as diphenyl sulfide, dibenzofuran,thianthrene, phenoxathin, dibenzodioxine, phenodioxin, diphenylene,4,4'-diphenoxybiphenyl, xanthone, 2,2'-diphenoxybiphenyl,1,4-diphenoxybenzene, 1,3-diphenoxybenzene, 1-phenoxynapthalene,1,2-diphenoxynapthalene, diphenoxybenzophenone, diphenoxy dibenzoylbenzene, diphenyl ether, 1,5-diphenoxynapthalene, and the like. Amongthese, diphenyl ether, diphenyl, diphenyl methane, 1,4-diphenoxybenzene, and 4,4'-diphenoxy diphenyl ether are preferred.

Similarly, the following compounds are diacyl halides which may be usedas reactants: terephthaloyl chloride, isophthaloyl chloride,thio-bis(4,4'-benzoyl chloride), benzophenone-4,4'-di(carbonylchloride), oxy-bis(3,3'-benzoyl chloride), diphenyl-3,3'-di(carbonylchloride), carbonyl-bis(3,3'-benzoyl chloride),sulfonyl-bis(4,4'-benzoyl chloride), sulfonyl-bis(3,3'-benzoylchloride), sulfonyl-bis(3,4'-benzoyl chloride), thio-bis(3,4'-benzoylchloride), diphenyl-3,4'-di(carbonyl chloride),oxy-bis[4,4'-(2-chlorobenzoyl chloride)], naphthalene-1,6-di(carbonylchloride), napthalene-1,5-di(carbonyl chloride),naphthalene-2,6-di(carbonyl chloride),oxy-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)],thio-bis[8,8'-naphthalene-1,1-di(carbonyl chloride)],[7,7'-binaphthyl-2,2'-di(carbonyl chloride)], diphenyl-4,4'-di(carbonylchloride), carbonyl-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)],sulfonyl-bis[6,6'-napthalene-2,2'-di(carbonyl chloride)],dibenzofuran-2,7-di(carbonyl chloride) and the like.

Illustrative of suitable acyldihalides include carbonyl chloride(phosgene), carbonyl bromide, carbonyl fluoride and oxaloyl chloride.

Preferably, diphenyl ether and/or diphenoxybenzene are reacted withterephthaloyl chloride.

Fluorobenzene and p-fluorobenzoyl chloride, as end-capping agents, havebeen selected for illustration purposes only. It should be noted thatother similar aromatic compounds, e.g. ##STR24## and materials whereinthe fluoride is replaced by chloride, bromide, or nitro can be similarlyused. Fluorobenzene and p-fluorobenzoyl chloride are preferred.

Self condensation of the following halo-aromatic halides

    H--Ar"--COY

wherein Ar" is a divalent aromatic radical and H is an aromaticallybound hydrogen atom, Y is as defined above, and COY is an aromaticallybound acyl halide group which monoacyl halide is self-polymerizable,offers yet another route to these halo-terminated precursors; an examplefollows: ##STR25##

The preferred Friedel-Crafts catalysts are aluminum chloride, antimonypentachloride and ferric chloride. Other Friedel-Crafts catalysts, suchas aluminum bromide, boron trifluoride, zinc chloride, antimonytrichloride, ferric bromide, titanium tetrachloride, and stanicchloride, can also be used. In the preferred embodiment, excess of up to100 mole percent of the acid catalyst is used.

The polymerization is generally carried out in the presence of asolvent. The preferred organic solvent is 1,2-dichloroethane. Othersolvents such as symmetrical tetrachloroethane, o-dichlorobenzenehydrogen fluoride, methylene chloride, trichloromethane,trichloroethylene, or carbon disulfide may be employed. Cosolvents suchas nitromethane, nitropropane, dimethyl formamide, sulfolane, etc. maybe used. Concentrations as low as 3 to as high as 40 wt. percent may beused. Generally lower concentrations are preferred when high molecularweight polymers are being prepared. Higher concentrations are preferablyused when oligomers are prepared.

The reaction may be carried out over a range of temperatures which arefrom about -40° C. to about 160° C. In general, it is preferred to carryout the reaction at a temperature in the range of 0° to 30° C. In somecases it is advantageous to carry out the reaction at temperatures above30° C. or below 0° C. Most preferably, the reactions are carried out attemperatures below 0° C. The reaction may be carried out at atmosphericpressure although higher or lower pressures may be used. Reaction timesvary depending on the reactants, etc. Generally, reaction times of up to6 hours and longer are preferred.

(B) Hydroxyl terminated precursors

Basic hydrolysis using methods known in the art (for example in amixture of dimethyl sulfoxide and water, diphenyl sulfone and water,aqueous amide aprotic solvents) of the dihalo oligomers should yield thedihydroxy oligomers.

(C) Hydroxyl-Halogen-terminated precursors

Methods very similar to those described under (I)(C) are useful, i.e.

(i) Partial hydrolysis of the dihalo-precursors.

(ii) Reaction of the dihalo-precursor with a diphenol under nucleophilicsubstitution conditions.

(iii) Reaction of the dihydroxy precursor with an activateddihalobenzenoid compound under conditions of nucleophilic substitution.

(III) Non-functionalized precursors

Using the Friedel-Crafts reaction described above, non-functionalizedprecursors can be prepared. An example is as follows: ##STR26##

Obviously, a wide variety of such oligomers are possible by theappropriate selection of the monomers listed above.

Preparation of the Block Copolymers Situation (I)

The block copolymers may be prepared by a nucleophilic reaction betweenpreformed precursors or polymers having mutually reactive groups asfollows:

    nA+nB→(AB).sub.n

there may be more than two precursors or polymers, used to form theblock copolymers, i.e.,:

    nA+nB+nC→(ABC).sub.n

The precursors or polymers may be illustrated by the following:##STR27## where X is an aryl halide, preferably chlorine or fluorine,and is ortho or para to ##STR28## and ##STR29## The reaction of thesetwo precursors or polymers forms the block copolymer (AB)_(n)Alternatively, the precursors or polymers may be illustrated by thefollowing: ##STR30##

Their condensation will yield a block copolymer.

Another alternative is the following: ##STR31## which can be reactedwith a monomeric material, i.e.,

    HO--monomer--OH

to give the copolymer; or ##STR32## which can be reacted with amonomeric material, i.e.,

    X--monomer--X

to give the copolymer.

If A and B are identical their coupling (e.g., the last two cases) mustbe performed with a difunctional oligomeric agent, i.e,: ##STR33## or

    X--OLIGOMER--X

Specific examples are as follow: ##STR34##

The precursors (F) and (G) are prepared using the nucleophilic route. Anelectrophilically prepared, fluorine-terminated starting material is,for example, the following: ##STR35##

The preparation of an oligomeric coupling agent is illustrated below:##STR36##

The equation below illustrates the coupling of two identical blocksusing an oligomeric agent: ##STR37##

Another oligomer that can be prepared is the following: ##STR38## thisoligomer is prepared in the same manner as oligomer (F) except that anexcess of 4,4'-difluorobenzophenone is used.

The reaction of (J) with (G) in the presence of HO--ph--O--ph--OH willyield a coupled polymer having different blocks.

The reactions are carried out by heating a mixture of the said precursoror precursors with the appropriate monomers (if required) at atemperature of from about 100° to about 400° C. The reactions areconducted in the presence of an alkali metal carbonate or bicarbonate.Preferably a mixture of alkali metal carbonates or bicarbonates is used.When a mixture of alkali metal carbonates or bicarbonates is used, themixture comprises sodium carbonate or bicarbonate with a second alkalimetal carbonate or bicarbonate wherein the alkali metal of the secondcarbonate or bicarbonate has a higher atomic number than that of sodium.The amount of the second alkali metal carbonate or bicarbonate is suchthat there is from 0.01 to about 0.25 gram atoms of the second alkalimetal per gram atom of sodium. Of course, it is possible to use thepreformed alkali metal salts of diphenols.

The higher alkali metal carbonates or bicarbonates are thus selectedfrom the group consisting of potassium, rubidium and cesium carbonatesand bicarbonates. Preferred combinations are sodium carbonate orbicarbonate with potassium carbonate or cesium carbonate.

The alkali metal carbonates or bicarbonates should be anhydrousalthough, if hydrated salts are employed, where the polymerizationtemperature is relatively low, e.g. 100° to 250° C., the water should beremoved, e.g. by heating under reduced pressure, prior to reaching thepolymerization temperature.

Where high polymerization temperatures (>250° C.) are used, it is notnecessary to dehydrate the carbonate or bicarbonate first as any wateris driven off rapidly before it can adversely affect the course of thepolymerization reaction.

The total amount of alkali metal carbonate or bicarbonate employedshould be such that there is at least 1 atom of alkali metal for eachphenol group. Hence, when using an oligomeric diphenol there should beat least 1 mole of carbonate, or 2 moles of bicarbonate, per mole of thearomatic diol. Likewise where an oligomeric halophenol is employed thereshould be at least 0.5 mole of carbonate, or 1 mole of bicarbonate, permole of the halophenol.

An excess of carbonate or bicarbonate may be employed. Hence there maybe 1 to 1.2 atoms of alkali metal per phenol group. While the use of anexcess of carbonate or bicarbonate may give rise to faster reactions,there is the attendant risk of cleavage of the resulting polymer,particularly when using high temperatures and/or the more activecarbonates.

As stated above the amount of the second (higher) alkali metal carbonateor bicarbonate employed is such that there are 0.001 to about 0.2 gramsatoms of the alkali metal of higher atomic number per gram atom ofsodium.

Thus when using a mixture of carbonates, e.g. sodium carbonate andcesium carbonate, there should be 0.1 to about 20 moles of cesiumcarbonate per 100 moles of sodium carbonate. Likewise when using amixture of a bicarbonate and a carbonate, e.g. sodium bicarbonate andpotassium carbonate, there should be 0.05 to 10 moles of potassiumcarbonate per 100 moles of sodium bicarbonate.

A mixed carbonate, for example sodium and potassium carbonate, may beemployed as the second alkali metal carbonate. In this case, where oneof the alkali metal atoms of the mixed carbonate is sodium, the amountof sodium in the mixed carbonate should be added to that in the sodiumcarbonate when determining the amount of mixed carbonate to be employed.

Preferably, from 0.001 to 0.2 gram atoms of the alkali metal of thesecond alkali metal carbonate or bicarbonate per gram atom of sodium isused.

Where an oligomeric bisphenol and oligomeric dihalobenzenoid compoundare employed, they should be used in substantially equimolar amounts. Anexcess of one over the other leads to the production of lower molecularweight products. However a slight excess, up to 5 mole %, of thedihalide may be employed if desired.

The reaction is carried out in the presence of an inert solvent.Preferably, the solvent is an aliphatic or aromatic sulphoxide orsulphone of the following formula ##STR39## where x is 1 or 2 and R andR' are alkyl or aryl groups and may be the same or different. R and R'may together form a divalent radical. Preferred solvents includedimethyl sulphoxide, dimethyl sulphone, sulpholane (1,1 dioxothiolan),or aromatic sulphones of the formula: ##STR40## where R₂ is a directlink, an oxygen atom or two hydrogen atoms (one attached to each benzenering) and R₃ and R'₃, which may be the same or different, are hydrogenatoms and alkyl or phenyl groups. Examples of such aromatic sulphonesinclude diphenylsulphone, dibenzothiophen dioxide, phenoxathiin dioxideand 4-phenylsulphonyl biphenyl. Diphenylsulphone is the preferredsolvent. Other solvents that may be used include benzophenone,N,N'-dimethyl acetamide, N,N-dimethyl formamide andN-methyl-2-pyrrolidone.

The polymerization temperature is in the range of from about 100° toabout 400° C. and will depend on the nature of the reactants and thesolvent, if any, employed. The preferred temperature is above 270° C.The reactions are generally performed under atmospheric pressure.However, higher or lower pressures may be used.

For the production of some polymers, it may be desirable to commencepolymerization at one temperature, e.g. between 200° and 250° C. and toincrease the temperature as polymerization ensues. This is particularlynecessary when making polymers having only a low solubility in thesolvent. Thus, it is desirable to increase the temperature progressivelyto maintain the polymer in solution as its molecular weight increases.

To minimize cleavage reactions it is preferred that the maximumpolymerization temperature be below 350° C.

The polymerization reaction may be terminated by mixing a suitable endcapping reagent, e.g. a mono or polyfunctional halide such as methylchloride, difluorobenzophenone, monofluoro benzophenone,4,4'-dichlorodiphenylsulphone with the reaction mixture at thepolymerization temperature, heating for a period of up to one hour atthe polymerization temperature and then discontinuing thepolymerization.

This invention is also directed to an improved process for making theblock polymers. Specifically, this process is directed to preparingpoly(aryl ether ketone) precursors and the block polymer by the reactionof a mixture of at least one bisphenol and at least one dihalobenzenoidcompound, or a halophenol to make the precursor, or the reaction of theprecursor to make the block polymer either one or both in the presenceof a combination of sodium carbonate and/or bicarbonate an alkali metalhalide selected from potassium, rubidium, or cesium fluoride orchloride, or combinations thereof.

The reaction is carried out by heating a mixture of one or morebisphenols and one or more dihalobenzenoid compounds or halophenols orthe block precursor and other reactants, as described herein, at atemperature of from about 100° to about 400° C. The reaction isconducted in the presence of added sodium carbonate and/or bicarbonateand potassium, rubidium or cesium fluorides or chlorides. The sodiumcarbonate or bicarbonate and the chloride and fluoride salts should beanhydrous although, if hydrated salts are employed, where the reactiontemperature is relatively low, e.g. 100° to 250° C., the water should beremoved, e.g. by heating under reduced pressure, prior to reaching thereaction temperature.

Where high reaction temperatures (>250° C.) are used, it is notnecessary to dehydrate the carbonate or bicarbonate first as any wateris driven off rapidly before it can adversely affect the course of thereaction. Optionally, an entraining organic medium can be used to removewater from the reaction such as toluene, xylene, chlorobenzene, and thelike.

The total amount of sodium carbonate or bicarbonate and potassium,rubidium or cesium fluoride or chloride, or combinations thereofemployed should be such that there is at least 1 atom of total alkalimetal for each phenol group, regardless of the anion (carbonate,bicarbonate or halide). Likewise where a halophenol is employed thereshould be at least one mole of total alkali metal per mole ofhalophenol.

Preferably, from about 1 to about 1.2 atoms of sodium for each phenolgroup is used. In another preferred embodiment from 0.001 to about 0.5atoms of alkali metal (derived from a higher alkali metal halide) isused for each phenol group.

The sodium carbonate or bicarbonate and potassium fluoride are used suchthat the ratio of potassium to sodium therein is from about 0.001 toabout 0.5, preferably from about 0.01 to about 0.25, and most preferablyfrom about 0.02 to about 0.20.

An excess of total alkali metal may be employed. Hence there may beabout 1 to about 1.7 atoms of alkali metal per phenol group. While theuse of a large excess of alkali metal may give rise to faster reactions,there is the attendant risk of cleavage of the resulting polymer,particularly when using high temperatures and/or the more active alkalimetal salts. In this respect, cesium is a more active metal andpotassium is a less active metal so that less cesium and more potassiumare used. Further, the chloride salts are less active than the fluoridesalts so that more chloride and less fluoride is used.

Where a bisphenol and dihalobenzenoid compound are employed, they shouldbe used in substantially equimolar amounts when maximum molecular weightis sought. However a slight excess, up to 5 mole %, of dihalide may beemployed if desired. An excess of one over the other leads to theproduction of low molecular weight products which can be desirable whenthe process is directed to making lower molecular weight PAEK, forexample, the precursors for block polymer formation.

The reactions are carried out in the presence of an inert solvent.

The reaction temperature is in the range of from about 100° to about400° C. and will depend on the nature of the reactants and the solvent.The preferred temperature is above 250° C. The reactions are preferablycarried out at ambient pressure. However, higher or lower pressure canalso be used. The reaction is generally carried out in an inertatmosphere.

For the production of some block polymers it may be desirable tocommence reaction at one temperature, e.g. between 200° and 250° C. andto increase the temperature as reaction ensues. This is particularlynecessary when making high molecular weight polymers having only a lowsolubility in the solvent. Thus, there it is desirable to increase thetemperature progressively to maintain the polymer in solution as itsmolecular weight increases.

Situation (II)

The block copolymers of this invention may be prepared by a nucleophilicpolycondensation reaction between a precursor or polymer and one or moremonomers.

The various combinations possible in this situation are illustratedbelow: ##STR41## is reacted with

    X--monomer--X+HO--monomer--OH

to give the block copolymer; or ##STR42## is reacted with

    X--monomer--X+HO--monomer--OH

to yield the block copolymer.

IIc. Still another possibility is the following: ##STR43## is reactedwith ##STR44## is reacted with ##STR45## or ##STR46## is reacted with##STR47## is reacted with

    X--monomer--OH.

IId. Triblock copolymers could, for instance, be obtained via the routeshown ##STR48##

Such situations arise in particular where A and B have the samecomposition, or if the polymer block obtained form X-monomer-OH isidentical to one of the precursors.

Numerous other possibilities that are obvious to those skilled in theart exist.

Additionally, the block copolymer may be prepared from a preformedpolymer and an oligomer via coupling and transetherification. Theprocess conditions in Situation II are the same as discussed forSituation I.

Situation III

The block copolymers of this invention may also be prepared byFriedel-Crafts (electrophilic) polymerization techniques as fullydescribed above. The preparation of a block copolymer (AB)_(n) will beillustrated by the use of diphenyl ether and terephthaloyl chloride asfollows: ##STR49## Obviously, each oligomer can also be prepared in aseparate step and then reacted with the other oligomer.

Situation V

Poly(ether ketone) based block copolymers can be prepared by using thenon-functionlized oligomers of the type (X). Both nucleophilic andelectrophilic (Friedel-Crafts) condensation are possible.

(a) The nucleophilic polycondensation.

The solution condensation of hydroquinone and 4,4'-difluorobenzophenoneis the presence of oligomer (X) will yield a copolymer due to atransetherification process accompanying polymer formation. This isschematically represented as follows: ##STR50##

There are numerous possibilities for reagent selection; thus, a widenumber of structures is available.

(b) Electrophilic (Friedel-Crafts) Polycondensation.

Oligomer (X) or any other non-functional oligomer of the type ##STR51##can be made to react in a Friedel-Crafts polycondensation as shown belowusing terephthaloyl chloride and 1,4-diphenoxybenzene (wherein Ar andAr' are as defined above and Ar⁶ is a monovalent aryl group such asphenyl): ##STR52## where HAr'H is, for example, Ph--O--Ph and Ar is, forexample, Ph.

Obviously, once again, numerous possibilities exist and are obvious tothose skilled in the art. The various nucleophilically andelectrophilically prepared precursors listed above can all be utilizedin this variant.

The copolymers of this invention may include mineral fillers such ascarbonates including chalk, calcite and dolomite; silicates includingmica, talc, wollastonite; silicon dioxide; glass spheres; glass powders;aluminum; clay; quartz; and the like. Also, reinforcing fibers such asfiberglass, carbon fibers, organic polyamide fibers, and the like may beused. The copolymers may also include additives such as titaniumdioxide; thermal stabilizers, ultraviolet light stabilizers, processingaids, plasticizers, and the like.

The copolymers of this invention may be fabricated into any desiredshape, i.e., moldings, coatings, films, or fibers. They are particularlydesirable for use as electrical insulation for electrical conductors.

Also, the copolymers may be woven into monofilament threads which arethen formed into industrial fabrics by methods well known in the art asexemplified by U.S. Pat. No. 4,359,501. Further, the copolymers may beused to mold gears, bearings and the like.

Examples

The following examples serve to give specific illustrations of thepractice of this invention but they are not intended in any way to limitthe scope of this invention.

Example 1

A 2 liter, 3 neck, round bottom flask was equipped with a mechanicalstirrer, a nitrogen inlet, condenser and a thermometer. The flask wascharged with 19.28 g (0.095 moles) of terephthaloyl chloride, 1.02 g(0.005 moles) of isophthaloyl chloride, 0.42 g (0.003 moles) of benzoylchloride, 17.25 g (0.1015) moles of diphenyl ether and 700 mls of1,2-dichloroethane. This solution was cooled to 5° C. in an ice waterbath. Aluminum chloride (34.76 g, 0.260 moles) was added in portionswhile maintaining the temperature below 10° C. The resulting reactionmixture was held at 5°-10° C. for 6 hours. After -30 minutes aprecipitate formed. At the end of 6 hours the ice bath was removed andthe reaction mixture was allowed to warm to ambient temperatures (-25°C.) where it was held for an additional 16 hours. The reaction mixturewas poured into 3 liters of ice water containing 100 ml of concentratedhydrochloric acid. The resulting three phase system was heated to -85°C. to distill the 1,2-dichloroethane. The polymer was isolated byfiltration, washed with water (2×500 ml) and methanol (2×500 ml) anddried in a vacuum oven at 100° C. The product had a reduced viscosity of0.58 dl/g as measured in concentrated sulfuric acid at 25° C. and aconcentration of 1 g/100 ml.

EXAMPLE 2

A 250 ml glass resin reactor was equipped with a mechanical stirrer,nitrogen sparge tube, thermocouple, Dean Stark trap and condenser. Tothe reactor were charged, 16.35 g. (0.075 moles) of4,4'-difluorobenzophenone, 8.25 g (0.075 moles) of hydroquinone, 5.40 gof a crystalline polyaryletherketone prepared in Example 1 and havingthe structural repeat unit (XI), 7.70 g. (0.073 moles) of sodiumcarbonate, ##STR53##

(*wherein the CO groups are meta and para to each other)

0.53 g (0.004 moles) of potassium carbonate and 63 g of diphenylsulfone. The system was purged with nitrogen for 1 hour at roomtemperature and heated to 200° C. After 1 hour at 200° C. and 15 minutesat 250° C. the reaction was carried out at a temperature of 320° C. for1 hour. The viscous reaction mixture was poured hot from the reactor,allowed to solidify and then finely ground. The product was refluxed inacetone (700 ml), followed by 1N hydrochloric acid solution (700 ml); itwas then washed with water (2 times using 500 ml) and acetone (2 timesusing 500 ml) at room temperature. The product was dried in a vacuumoven at 100° C. for 24 hours. The final polymer had a reduced viscosityof 2.16 dl/g (in concentrated sulfuric acid at 1g/100 ml and 25° C.)C.sup. 13 nuclear magnetic resonance (nmr) spectroscopy indicated thepresence of the following blocks in the polymer: ##STR54##

EXAMPLE 3

A four neck 250 ml glass resin kettle was equipped with a mechanicalstirrer, nitrogen inlet, thermocouple and a Dean Stark trap with fittedcondenser. Into the kettle was charged 24.63 g (0.0765 moles) of1,4-bis(p-fluorobenzoyl)benzene, 8.25 g (0.0750 moles) of hydroquinone,7.70 g (0.0727 moles) of sodium carbonate, 0.53 g. (0.0038 moles) ofpotassium carbonate and 68.6 g of diphenyl sulfone. After purging thereaction mixture with nitrogen for 1 hour at room temperature, it washeated to 200° C. and held there for 1 hour. The temperature was raisedto 250° C. and held for 15 minutes and then to 320° C. for 2 hours. Thereaction mixture was poured into an aluminum pan, solidified and groundinto fine particles. The particles were refluxed in acetone for 1.5hours and in hydrochloric acid for 1.5 hours and then washed in ablender with water (2×500 ml) and acetone (2×500 ml). The resultingpolymer powder was dried in a vacuum oven overnight (about 12 hours) at100° C. The polymer had a reduced viscosity of 0.83 dl/g as measured inconcentrated sulfuric acid at 1g/100 ml and 25° C.

EXAMPLE 4

Example 2 was repeated except that the crystalline polyaryletherketone(XII) prepared in Example 3 and having the following structure ##STR55##was substituted for precursor (XI) in the initial charge. The finalblock copolymer had a reduced viscosity of 1.71 dl/g as measured inconcentrated sulfuric acid, 1g/100 ml at 25° C. and contained thefollowing blocks: ##STR56##

EXAMPLE 5

To the apparatus described in Example 2 were charged 32.20 g (0.100moles) of 1,4 bis (4-fluorobenzoyl) benzene, 11.01 g (0.100 moles) ofhydroquinone, 9.80 g of crystalline polyaryletherketone XI, 10.28 g(0.097 moles) of sodium carbonate, 0.69 g (0.005 moles) of potassiumcarbonate and 61.50 g of diphenyl sulfone. The reaction conditions andwork up were the same as in Example 1. The final block copolymer had areduced viscosity of 1.44 dl/g and contained the following blocks:##STR57##

EXAMPLE 6

A 250 ml 3-neck flask with slanted side arms fitted with a Claisen arm,nitrogen inlet tube, thermocouple probe, condenser, and stainless steelstirrer was charged with diflurobenzophenone (0.1104 mole, 24.09 gm),hydroquinone (0.115 mole, 12.66 gm), sodium carbonate (0.11/3 moles,12.43 gm, ground and dried), anhydrous potassium fluoride (0.0293 mole,1.70 gm) and diphenyl sulfone (100 gm). The apparatus was evacuated andfilled with argon by means of a Firestone valve connected to the top ofthe condenser. A flow of high purity nitrogen was begun and theconnection to the Firestone valve was replaced with a bubbler. Thecontents of the flask was heated carefully by means of a heating mantleand temperature controller to melt the diphenyl sulfone. The reactionmixture was stirred and heated to 200° C. and held 30 minutes, held at250° C. for 1 hour, and finally at 270° C. for 2 hours. The reactionmixture was poured from the reaction flask, cooled, ground to a finepowder, and a sample refluxed successively twice with acetone, once with2% hydrochloric acid, once with water, and washed thoroughly withacetone. The dried (120°, vacuum oven) sample gave a reduced viscosity(1% in conc. sulfuric acid, 25° C.) of 0.53 dl/gm. Based on reactantstoichiometry this oligomer had the following structure: ##STR58##

EXAMPLE 7

The oligomer was prepared essentially as in Example 6 except lesspotassium fluoride (0.01465 moles, 0.85 gm) was used and the reactionmixture was heated at 200° for 30 minutes, at 250° C. for 1 hour, andthen at 290° C. for 2 hours. The isolated oligomer had a reducedviscosity of 0.51 dl/gm (concentrated sulfuric acid, 1gm/100 ml at 25°C.).

EXAMPLE 8

A 2000 ml flask was fitted with a mechanical stirrer, nitrogen spargetube, thermometer, reflux condenser and gas outlet connected to anaqueous sodium hydroxide trap. The apparatus was purged with nitrogenand while under a positive pressure was charged with 1400 ml of1,2-dichloroethane, 2.03 g (0.010 moles) of isophthaloyl chloride, 38.57g (0.190 moles) of terephthaloyl chloride, 35.74 g (0.210 moles) ofdiphenylether and 3.17 g (0.020) moles of p-fluorobenzoyl chloride. Themixture was cooled to 0° C. as 12.80 g (0.546 moles) of aluminumtrichloride was added at a rate such as not to exceed 5° C. After 6hours at 0° C., the heterogeneous slurry was allowed to warm to roomtemperature (about 25° C.) and stirred for an additional 17 hours. Theexcess solvent was decanted and the precipitate was added to diluteaqueous acid (3000 ml H₂ O/100 ml hydrochloric acid conc.) and heated toreflux for 2 hours while the 1,2-dichloroethane was continuouslyremoved. The polymer was filtered and dried in a vacuum at 60° C. for 24hours to give 60.2 grams of the final polymer having a general structureas shown in formula (IV). The polymer had a reduced viscosity of 0.34dl/g as measured in sulfuric acid at a concentration of 1 g/100 ml at25° C. ##STR59##

EXAMPLE 9

A 250 ml glass resin reactor was equipped with a mechanical stirrer,nitrogen sparge tube, thermocouple, Dean Stark trap, condenser and apressure equalizing dropping funnel. To the reactor were charged 16.51 g(0.076 moles) of 4,4'difluorobenzophenone, 5.41 g of a difluoro endcapped crystalline poly(aryl ether ketone) prepared as in Example 8,8.25 gms (0.075 moles) of hydroquinone, 7.70 g (073 moles) of sodiumcarbonate, 0.53 g (0.004 moles) of potassium carbonate, 63 g of diphenylsulfone and xylene. The apparatus was evacuated then charged withnitrogen. This procedure was repeated 3 additional times. While beingcontinuously purged with nitrogen, the mixture was heated to 200° C. for1 hour followed by 15 minutes at 250° C.During this time the xylene wascontinuously replenished. The reaction was carried out at a temperatureof 320° C. for 1 hour resulting in a viscous reaction mixture which waspoured hot from the reactor, allowed to solidify, and then groundfinely. The product was refluxed in acetone (700 ml), followed by 1Naqueous hydrochloric acid solution (700 ml). It was then washed withwater (5 times using 500 ml) at room temperature. The product was driedin a vacuum oven at 100° C. for 24 hours. The final polymer had areduced viscosity of 1.34 dl/g (in concentrated sulfuric acid at 1 g/100ml and 25° C.).

EXAMPLE 10

A 1000 ml flask was fitted with a mechanical stirrer, reflux condenser,thermometer, nitrogen sparge tube, and gas outlet connected to anaqueous sodium hydroxide trap. The apparatus was purged with nitrogenand while under a positive pressure was charged with 85.11 g (0.500moles) of diphenylether, 68.01 g (0.335 moles) of terephthaloylchloride, 53.12 g (0.335 moles) of p-fluorobenzoyl chloride and 600 mlsof 1,2-dichloroethane. The mixture was cooled to 0° C. as 174.21 g (1.31moles) of aluminum trichloride was added at a rate such as not to exceed5° C. After 6 hours at 0° C. the viscous homogeneous mixture was allowedto warm to room temperature and stirring was continued for an additional17 hours. The entire mixture was then poured into dilute aqueous acid(3000 ml of H₂ O/100 ml hydrochloric acid conc.), refluxed withcontinuous removal of 1,2-dichloroethane and filtered. The precipitatewas refluxed in 5% hydrochloric acid (700 ml), filtered, washed at roomtemperature with distilled water (2 times using 500 ml) and methanol (2times using 500 ml) and dried in a vacuum at 100° C. for 24 hours. Thefinal oligomeric crystalline poly(aryletherketone) had the structuralformula (V) and was characterized by ¹³ C NMR, by mass spectroscopy andelemental analysis. ##STR60##

EXAMPLE 11

A 250 ml flask was fitted with a mechanical stirrer, nitrogen inlet,thermocouple-controller, Dean Stark trap with a condenser and anaddition funnel. The flask was charged with 11.01 gms (0.1000 moles) ofhydroquinone, 21.93 gms (0.1005 moles) of 4,4'-difluorobenzophenone,10.28 gms (0.0970 moles) of anhydrous sodium carbonate, 0.691 gms(0.0050 moles) of anhydrous potassium carbonate, 86.5 gms of diphenylsulfone, and 35 ml of xylene. The equipment was then evacuated andfilled with nitrogen (three times).

Heat was applied to raise the temperature to 200° C. for one hour, thetemperature was then raised to 250° C. and held for fifteen minutes, andraised to 320° C. The xylene addition was stopped and 7.21 gms of apoly(ether ketone) with a reduced viscosity of 1.46 dl/gm (measured insulfuric acid at a concentration of 1 g/100 ml at 25° C.) was added. Thepoly(ether ketone) was prepared by the aluminum chloride catalyzedcondensation of terepthaloyl chloride with diphenyl ether and a smallamount of benzoyl chloride. The polymerization was continued for onehour at 320° at which point the reaction mixture was very thick. Methylchloride (0.5 gms) was added through the nitrogen inlet (below theliquid surface) and the reaction mixture was then dumped into astainless steel pan.

The cooled solid mass was ground to a granular material which wasextracted with two portions of boiling acetone followed by two portionsof boiling water. After drying in vacuo, the reduced viscosity was 1.37dl/gm (1% in conc. sulfuric acid, 25° C.).

The polymer was compression molded (20 mil) and tested for tensilestrength and modulus according to ASTM D-638, elongation at breakaccording to ASTM D-638 and pendulum impact strength according to ASTMD-256. The results are as follows:

    ______________________________________                                        Tensile modulus (psi)   390,000                                               Tensile strength (psi)  13,000                                                Elongation at break (%) 6                                                     Pendulum impact (ft-lb/in.sup.3)                                                                      83                                                    ______________________________________                                    

EXAMPLE 12

A 500 ml flask was fitted with a mechanical stirrer, a nitrogen spargetube, thermometer, reflux condenser and gas outlet connected to anaqueous sodium hydroxide trap. The apparatus was purged with nitrogenand while under a positive pressure of nitrogen was charged with 11.40 g(0.067 moles) of diphenyl ether, 20.30 g (0.100 moles) of terephthaloylchloride and 270 ml of fluorobenzene. The mixture was cooled to 0° C. as34.67 g (0.260 moles) of aluminum trichloride was added at such a rateas not to exceed 5° C. After stirring at 0° C. for 6 hours the reactionmixture was allowed to warm to 25° C. and stirring continued for anadditional 17 hours. The resultant reaction mixture was poured intodilute aqueous acid (3000 ml water/100 ml hydrochloric acid conc.) andrefluxed with continuous removal of the excess fluorobenzene. Theresultant precipitate was filtered, refluxed in 5% hydrochloric acid(700 ml), filtered, washed with water (2 times using 500 ml), followedby methanol (2 times using 500 ml) at room temperature and dried invacuum at 100° C. for 24 hours. The final oligomeric crystallinepoly(aryl ether ketone) material having the structural formula (I) wasidentified by ¹³ C NMR and confirmed by mass spectroscopy. ##STR61##

EXAMPLE 13

A 500 ml flask was fitted with a mechanical stirrer, nitrogen spargetube, thermometer, reflux condenser, and gas outlet connected to anaqueous sodium hydroxide trap. The apparatus was purged with nitrogenand while under a positive pressure was charged with 40.60 g (0.200moles) of terephthaloyl chloride, 22.80 g (0.134 moles) of diphenylether and 220 mls of 1,2-dichloroethane. The resultant mixture wascooled to 0° C. as 69.34 g (0.520 moles) of aluminum trichloride wasadded at such a rate as not to exceed 5° C. After stirring for 6 hoursat 0° C. 25.75 g (0.268 moles) of fluorobenzene was added and themixture was allowed to warm to 25° C. and stirring continued for anadditional 17 hours. The entire mixture was then poured into diluteaqueous acid (3000 ml water/100 ml hydrochloric acid conc.) and refluxedwith the continuous removal of 1,2-dichloroethane and excessfluorobenzene. The resultant precipitate was collected via filtration,refluxed in 5% hydrochloric acid (700 ml), filtered, washed with water(2 times using 500 ml) followed by methanol (2 times using 500 ml) atroom temperature and dried in a vacuum at 100° C. for 24 hours. Thefinal oligomeric crystalline poly(aryl ether ketone) having thestructural formula (I) was characterized by ¹³ C NMR and confirmed bymass spectroscopy. ##STR62##

EXAMPLE 14

A 250 ml flask was fitted with a mechanical stirrer, nitrogen spargetube, thermometer, reflux condenser, and gas outlet connected to anaqueous sodium hydroxide trap. The apparatus was purged with nitrogenand while under positive pressure was charged with 96 ml of1,2-dichloroethane, 11.40 g (0.067 moles) of diphenyl ether, 20.30 g(0.100 moles) of terephthaloyl chloride and 6.44 g (0.067 moles) offluorobenzene. The mixture was cooled to 0° C. as 34.67 g (0.260 moles)of aluminum trichloride was added at such a rate as not to exceed 5° C.After 6 hours at 0° C. the heterogeneous slurry was allowed to warm toroom temperature and stirring was continued for an additional 17 hours.The entire mixture was then poured into dilute aqueous acid (300 mlwater/100 ml hydrochloric acid conc.) and refluxed for 2 hours with thecontinuous removal of 1,2-dichloroethane. The resultant precipitate wascollected via filtration, refluxed in 5% hydrochloric acid (700 ml),filtered, washed in a blender with distilled water (2 times using 500ml) followed by methanol (2 times using 500 ml) at room temperature anddried in a vacuum at 100° C. for 24 hours. The final oligomericcrystalline poly(aryl ether ketone) having the structural formula (I)was characterized by ¹³ C NMR and confirmed by mass spectroscopy.##STR63##

EXAMPLE 15

A 100 ml flask was fitted with a mechanical stirrer, reflux condenser,thermometer, nitrogen sparge, and gas outlet connected to an aqueoussodium hydroxide trap. The apparatus was purged with nitrogen and whileunder a positive pressure was charged with 17.02 g (0.100 moles) ofdiphenyl ether, 10.15 g (0.050 moles) of terephthaloyl chloride, 15.86 g(0.100 moles) of p-fluorobenzoyl chloride and 48 mls of1,2-dichloroethane. The mixture was cooled to 0° C. as 34.67 g (0.260moles) of aluminum trichloride was added at such a rate as not to exceed5° C. After 6 hours at 0° C. the viscous homogeneous mixture was allowedto warm to room temperature and stirring continued for an additional 17hours. The entire mixture was then poured into dilute aqueous acid (1300ml water/50 ml hydrochloric acid conc.), refluxed with continuousremoval of 1,2-dichloroethane, and filtered. The precipitate wasrefluxed in 5% hydrochloric acid (700 ml), filtered, washed at roomtemperature with water (2 times using 500 ml) and methanol (2 timesusing 500 ml) and dried in a vacuum at 100° C. for 24 hours. The finaloligomeric crystalline poly(aryl ether ketone) having the structuralformula (I) was characterized by ⁻⁻ C NMR and confirmed by massspectroscopy and elemental analysis. ##STR64##

EXAMPLE 16

A 500 ml flask was fitted with a mechanical stirrer, reflux condenser,thermometer, nitrogen sparge tube, and gas outlet fitted to an aqueoussodium hydroxide trap. The apparatus was charged with 185 ml ofo-dichlorobenzene, 34.04 g (0.20 moles) of diphenyl ether, 27.20 g(0.134 moles) of terephthaloyl chloride, 21.25 g (0.134 moles) ofp-fluorobenzoyl chloride and 29.39 g (0.402 moles) of N N-dimethylformamide. The mixture was cooled to 0° C. as 139.37 g (1.045 moles) ofaluminum trichloride was added at such a rate as not to exceed 20° C.After completion of the addition, the mixture was warmed to roomtemperature and stirring continued for an additional 17 hours. Theentire mixture was then added to stirring methanol (1.5 l), filtered,added to delute aqueous acid (3000 ml water/100 ml hydrochloric acidconc.) and refluxed for 2 hours. The resultant precipitate was collectedby filtration and washed in a blender with water (2 times 500 ml),methanol (2 times 500 ml), filtered and dried in a vacuum at 100° C. for24 hours. The final oligomer having the structural formula (I) wascharacterized by ¹³ C NMR and confirmed by mass spectroscopy. ##STR65##

EXAMPLE 17

A 500 ml flask was fitted with a mechanical stirrer, reflux condenser,nitrogen sparge tube, thermometer and gas outlet connected to an aqueoussodium hydroxide trap. The apparatus was purged with nitrogen and whileunder a positive pressure was charged with 220 ml of 1,2-dichloroethane,27.20 g (0.134 moles) of terephthaloyl chloride, 34.04 g (0.200 moles)of diphenyl ether, 21.25 g (0.134 moles) of p-fluorobenzoyl chloride,and 96.62 g (0.804 moles) of sulfolane. The mixture was cooled to 0° C.as 187.61 g (1.407 moles) of aluminum trichloride was added at such arate as not to exceed 5° C. After 6 hours at 0° C., the viscoushomogeneous reaction mixture was allowed to warm to room temperature andstirring continued for an additional 17 hours. The entire mixture wasthen poured into dilute aqueous acid (3000 ml water/100 ml hydrochloricacid conc.) and heated to reflux for 2 hours while the 1,2-dichlroethanewas continuously removed. The resultant precipitate was collected byfiltration, then added to 5% hydrochloric acid and refluxed for 2 hours,filtered, washed in a blender with water (2 times using 500 ml) andmethanol (2 times using 500 ml), then dried in a vacuum at 100° C. for24 hours. The final oligomer having the structure formula (I) wascharacterized by ¹³ C NMR and conformed by mass spectroscopy andchemical analysis. ##STR66##

EXAMPLE 18

A 1000 ml flask was fitted with a mechanical stirrer, nitrogen spargetube, thermocouple, reflux condenser and gas outlet connected to anaqueous sodium hydroxide trap. The apparatus was purged with nitrogenand while under a positive pressure was charged with 700 ml of1,2-dichloroethane, 1.02 g (0.005 moles) of isophthaloyl chloride, 19.28g (0.095 moles) of terephthaloyl chloride, 17.87 g (0.105 moles) ofdiphenyl ether, 1.59 g (0.010 moles) of p-fluorobenzoyl chloride, and50.47 (0.420 moles) of sulfolane. The mixture was cooled to 0° C. as98.00 g (0.735 moles) of aluminum trichloride was added at such a rateas not to exceed 5° C. After 6 hours at 0° C. the deep red solution wasallowed to warm to room temperature and stirring continued for anadditional 17 hours. The entire reaction mixture was poured into diluteaqueous acid (3000 ml water/100 ml hydrochloric acid conc.) and heatedto reflux for 2 hours while the 1,2-dichloroethane was continuouslyremoved. The final polymer was filtered and dried in a vacuum at 60° C.for 24 hours to give 30.60 grams of the final polymer having a reducedviscosity of 0.35 dl/g as measured in concentrated sulfuric acid (1g/100 ml) at 25° C.

What is claimed is:
 1. A dihalo terminated precursor of the followingformula:

    X--Ar.sub.3 --(Ar.sub.1 --O--Ar.sub.2 --CO).sub.n --Ar.sub.4 --X

wherein X is halogen, Ar₁ and Ar₂ are divalent aromatic radialsoptionally containing solely an ether and/or a carbonyl function, Ar₃ isAr₄ CO, Ar₄ is 1,4 or 1,2 phenylene, and n is such that the molecularweight is below about 10,000.
 2. A dihydroxy terminated precursor of thefollowing formula: ##STR67## wherein Ar₁ and Ar₂ are divalent aromaticradicals optionally containing solely an ether and/or a carbonylfunction and n is such that the molecular weight is below about 10,000.3. A diacid halide terminated precursor of the following formula:##STR68## wherein X is halogen, Ar₁ and Ar₂ are divalent aromaticradicals optionally containing solely an ether and/or a carbonylfunction, Ar₃ is Ar₄ CO, Ar₄ is 1,4 or 1,2 phenylene and n is such thatthe molecular weight is below about 10,000.
 4. A diacid halideterminated precursor as defined in claim 3 of the following formula:##STR69## wherein Ph is a phenyl or a 1,4 phenylene unit.
 5. A diacidhalide terminated precursor as defined in claim 3 of the followingformula: ##STR70## wherein Ph is a phenyl or a 1,4 phenylene unit.
 6. Aprecursor of the following formula: ##STR71## wherein X is halogen, Ar₁and Ar₂ are divalent aromatic radicals optionally containing solely anether and/or a carbonyl function, Ar₃ is Ar₄ CO, Ar₄ is 1,4 or 1,2phenylene and n is such that the molecular weight is below about 10,000.7. A dihalo terminated precursor as defined in claim 1 of one of thefollowing formula: ##STR72## wherein Ph is a phenyl or a 1,4 phenyleneunit.
 8. A dihydroxy terminated precursor as defined in claim 2 of oneof the following formula: ##STR73## wherein Ph is a phenyl or a 1,4phenylene unit.
 9. A compound of the formula: ##STR74## wherein Ph is aphenyl or a 1,4-phenylene unit.
 10. A compound of the formula: ##STR75##wherein Ph is a phenyl or a 1,4-phenylene unit.
 11. A chain-extendingcompound of the following formula: ##STR76## wherein Ph is a phenyl or a1,4-phenylene unit.